Structural Transformations, Composition Anomalies and a Dramatic Collapse of Linear Polymer Chains in Dilute Ethanol-Water Mixtures

Water-ethanol mixtures exhibit many interesting anomalies, such as negative excess partial molar volume of ethanol, excess sound absorption coefficient at low concentrations, and positive deviation from Raoult's law for vapor pressure, to mention a few. These anomalies have been attributed to different, often contradictory origins, but a quantitative understanding is still lacking. We show by computer simulation and theoretical analyses that these anomalies arise from the sudden emergence of a bicontinuous phase that occurs at a relatively low ethanol concentration of x(eth) approximate to 0.06-0.10 (that amounts to a volume fraction of 0.17-0.26, which is a significant range!). The bicontinuous phase is formed by aggregation of ethanol molecules, resulting in a weak phase transition whose nature is elucidated. We find that the microheterogeneous structure of the mixture gives rise to a pronounced nonmonotonic composition dependence of local compressibility and nonmonotonic dependence in the peak value of the radial distribution function of ethyl groups. A multidimensional free energy surface of pair association is shown to provide a molecular explanation of the known negative excess partial volume of ethanol in terms of parallel orientation and hence better packing of the ethyl groups in the mixture due to hydrophobic interactions. The energy distribution of the ethanol molecules indicates additional energy decay channels that explain the excess sound attenuation coefficient in aqueous alcohol mixtures. We studied the dependence of the solvation of a linear polymer chain on the composition of the water-ethanol solvent. We find that there is a sudden collapse of the polymer at x(eth) approximate to 0.05-a phenomenon which we attribute to the formation of the microheterogeneous structures in the binary mixture at low ethanol concentrations. Together with recent single molecule pulling experiments, these results provide new insight into the behavior of polymer chain and foreign solutes, such as enzymes, in aqueous binary mixtures.

Partition function for hindered, one-and multi-dimensional rotors

Writing the hindered rotor (hr) partition function as the trace of (rho) over cap = e(-beta(H) over cap hr), we approximate it by the sum of contributions from a set of points in position space. The contribution of the density matrix from each point is approximated by performing a local harmonic expansion around it. The highlight of this method is that it can be easily extended to multidimensional systems. Local harmonic expansion leads to a breakdown of the method a low temperatures. In order to calculate the partition function at low temperatures, we suggest a matrix multiplication procedure. The results obtained using these methods closely agree with the exact partition function at all temperature ranges. Our method bypasses the evaluation of eigenvalues and eigenfunctions and evaluates the density matrix for internal rotation directly. We also suggest a procedure to account for the antisymmetry of the total wavefunction in the same. (C) 2012 Elsevier B.V. All rights reserved.

Structural, EPR, photo and thermoluminescence properties of ZnO:Fe nanoparticles

Zn(1-x)Fe(x)O(1+0.5x) (x = 0.5-5 mol%) nanoparticles were synthesized by a low temperature solution combustion route. The structural characterization of these nanoparticles by PXRD, SEM and TEM confirmed the phase purity of the samples and indicated a reduction in the particle size with increase in Fe content. A small increase in micro strain in the Fe doped nanocrystals is observed from W-H plots. EPR spectrum exhibits an intense resonance signal with effective g values at g approximate to 2.0 with a sextet hyperfine structure (hfs) besides a weak signal at g approximate to 4.13. The signal at g approximate to 2.0 with a sextet hyperfine structure might be due to manganese impurity where as the resonance signal at g approximate to 4.13 is due to iron. The optical band gap E-g was found to decrease with increase of Fe content. Raman spectra exhibit two non-polar optical phonon (E-2) modes at low and high frequencies at 100 and 435 cm(-1) in Fe doped samples. These modes broaden and disappear with increase of Fe do pant concentration. TL measurements of gamma-irradiated (1-5 kGy) samples show a main glow peak at 368 degrees C at a warming rate of 6.7 degrees Cs-1. The thermal activation parameters were estimated from Glow peak shape method. The average activation energy was found to be in the range 0.34-2.81 eV. (C) 2012 Elsevier B.V. All rights reserved.

Characterisation of microstructure and evaluation of optical and EPR properties of superhydrophobic copper dodecanoate films

Copper dodecanoate films prepared by emulsion method exhibit superhydrophobic property with water contact angle of 155 degrees and sliding angle of <2 degrees. The films have been characterised by using X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy techniques. Surface microstructure of copper dodecanoate consists of numerous microscale papillas of about 6-12 mu m in length with a diameter in the range of 360-700 nm. The superhydrophobicity of the films is due to their dual micronano surface morphology. The wetting behaviour of the film surface was studied by a simple water immersion test. The results show that copper dodecanoate film retained superhydrophobic property even after immersing in water for about 140 h. The optical absorption spectrum exhibits two broadbands centred at 388 and 630 nm that have been assigned to B-2(1g) -> E-2(g) and B-2(1g) -> B-2(2g) transitions of Cu2+ ions, respectively. The electron paramagnetic resonance spectrum exhibits two resonance signals with effective g values at g(parallel to)approximate to 2.308 and g(perpendicular to) approximate to 2.071, which suggests that the unpaired electron occupies d(x2-y2) orbital in the ground state. Copyright (C) 2011 John Wiley & Sons, Ltd.

Cause and Effect of Feedback: Multiphase Gas in Cluster Cores Heated by AGN Jets

Multiwavelength data indicate that the X-ray-emitting plasma in the cores of galaxy clusters is not cooling catastrophically. To a large extent, cooling is offset by heating due to active galactic nuclei (AGNs) via jets. The cool-core clusters, with cooler/denser plasmas, show multiphase gas and signs of some cooling in their cores. These observations suggest that the cool core is locally thermally unstable while maintaining global thermal equilibrium. Using high-resolution, three-dimensional simulations we study the formation of multiphase gas in cluster cores heated by collimated bipolar AGN jets. Our key conclusion is that spatially extended multiphase filaments form only when the instantaneous ratio of the thermal instability and free-fall timescales (t(TI)/t(ff)) falls below a critical threshold of approximate to 10. When this happens, dense cold gas decouples from the hot intracluster medium (ICM) phase and generates inhomogeneous and spatially extended Ha filaments. These cold gas clumps and filaments ``rain'' down onto the central regions of the core, forming a cold rotating torus and in part feeding the supermassive black hole. Consequently, the self-regulated feedback enhances AGN heating and the core returns to a higher entropy level with t(TI)/t(ff) > 10. Eventually, the core reaches quasi-stable global thermal equilibrium, and cold filaments condense out of the hot ICM whenever t(TI)/t(ff) less than or similar to 10. This occurs despite the fact that the energy from AGN jets is supplied to the core in a highly anisotropic fashion. The effective spatial redistribution of heat is enabled in part by the turbulent motions in the wake of freely falling cold filaments. Increased AGN activity can locally reverse the cold gas flow, launching cold filamentary gas away from the cluster center. Our criterion for the condensation of spatially extended cold gas is in agreement with observations and previous idealized simulations.

Coupled phonons, magnetic excitations, and ferroelectricity in AlFeO3: Raman and first-principles studies

We determine the nature of coupled phonons and magnetic excitations in AlFeO3 using inelastic light scattering from 5 to 315 K covering a spectral range from 100 to 2200 cm(-1) and complementary first-principles density functional theory-based calculations. A strong spin-phonon coupling and magnetic ordering-induced phonon renormalization are evident in (1) anomalous temperature dependence of many modes with frequencies below 850 cm(-1), particularly near the magnetic transition temperature T-c approximate to 250 K, and (2) distinct changes in band positions of high-frequency Raman bands between 1100 and 1800 cm(-1); in particular, a broad mode near 1250 cm(-1) appears only below T-c, attributed to the two-magnon Raman scattering. We also observe weak anomalies in the mode frequencies similar to 100 K due to a magnetically driven ferroelectric phase transition. Understanding of these experimental observations has been possible on the basis of first-principles calculations of the phonons' spectrum and their coupling with spins.

Thermoluminescence and EPR studies of nanocrystalline Nd2O3:Ni2+ phosphor

Nanocrystalline Nd2O3:Ni2+ (2 mol%) phosphor has been prepared by a low temperature (similar to 400 degrees C) solution combustion method, in a very short time (<5 min). Powder X-ray diffraction results confirm the single hexagonal phase of nanopowders. Scanning electron micrographs show that nanophosphor has porous nature and the particles are agglomerated. Transmission electron microscopy confirms the nanosize (20-25 nm) of the crystallites. The electron paramagnetic resonance (EPR) spectrum exhibits a symmetric absorption at g approximate to 2.77 which suggests that the site symmetry around Ni2+ ions is predominantly octahedral. The number of spins participating in resonance (N) and the paramagnetic susceptibility (chi) has been evaluated. Raman study show major peaks, which are assigned to F-g and combination of A(g) + E-g modes. Thermoluminescence (TL) studies reveal well resolved glow peaks at 169 degrees C along with shoulder peak at around 236 degrees C. The activation energy (E in eV), order of kinetics (b) and frequency factor (s) were estimated using glow peak shape method. It is observed that the glow peak intensity at 169 degrees C increases linearly with gamma-dose which suggest that Nd2O3:Ni2+ is suitable for radiation dosimetry applications. (C) 2012 Elsevier B.V. All rights reserved.

Piecewise Linearization Technique for Compact Charge Modeling of Independent DG MOSFET

Charge linearization techniques have been used over the years in advanced compact models for bulk and double-gate MOSFETs in order to approximate the position along the channel as a quadratic function of the surface potential (or inversion charge densities) so that the terminal charges can be expressed as a compact closed-form function of source and drain end surface potentials (or inversion charge densities). In this paper, in case of the independent double-gate MOSFETs, we show that the same technique could be used to model the terminal charges quite accurately only when the 1-D Poisson solution along the channel is fully hyperbolic in nature or the effective gate voltages are same. However, for other bias conditions, it leads to significant error in terminal charge computation. We further demonstrate that the amount of nonlinearity that prevails between the surface potentials along the channel actually dictates if the conventional charge linearization technique could be applied for a particular bias condition or not. Taking into account this nonlinearity, we propose a compact charge model, which is based on a novel piecewise linearization technique and shows excellent agreement with numerical and Technology Computer-Aided Design (TCAD) simulations for all bias conditions and also preserves the source/drain symmetry which is essential for Radio Frequency (RF) circuit design. The model is implemented in a professional circuit simulator through Verilog-A, and simulation examples for different circuits verify good model convergence.

A MATLAB Code for Three Dimensional Linear Elastostatics using Constant Boundary Elements

Present work presents a code written in the very simple programming language MATLAB, for three dimensional linear elastostatics, using constant boundary elements. The code, in full or in part, is not a translation or a copy of any of the existing codes. Present paper explains how the code is written, and lists all the formulae used. Code is verified by using the code to solve a simple problem which has the well known approximate analytical solution. Of course, present work does not make any contribution to research on boundary elements, in terms of theory. But the work is justified by the fact that, to the best of author’s knowledge, as of now, one cannot find an open access MATLAB code for three dimensional linear elastostatics using constant boundary elements. Author hopes this paper to be of help to beginners who wish to understand how a simple but complete boundary element code works, so that they can build upon and modify the present open access code to solve complex engineering problems quickly and easily. The code is available online for open access (as supplementary file for the present paper), and may be downloaded from the website for the present journal.

Structural, EPR, optical and Raman studies of Nd2O3:Cu2+ nanophosphors

Nanocrystalline Nd2O3:Cu2+ (2 mol %) phosphors have been prepared by a low temperature solution combustion technique. Powder X-ray diffraction (PXRD) results confirm that hexagonal A-type Nd2O3 (900 degrees C, 3 h) and the lattice parameters have been evaluated by Rietveld refinement. Surface morphology of as-formed and Cu2+ doped Nd2O3 phosphors show that the particles are irregular in shape and porous in nature. TEM results also confirm the nature and size of the particles. The EPR spectrum exhibits two resonance signals with effective g values at g(parallel to) approximate to 2.12 and g(perpendicular to) approximate to 2.04. The g values indicate that the site symmetry of Cu2+ ions is octahedral symmetry with elongated tetragonal distortion. Raman studies show major peaks, which are assigned, to F-g and combination of A(g) + E-g modes. It is observed that the Raman peaks and intensity have been reduced in Cu2+ doped samples. UV-Visible absorption spectra exhibit a strong and broad absorption band at similar to 240 nm. Further, the absorption peak shifts to similar to 14 nm in Cu2+ doped samples. The optical band gap is estimated to be 5.28 eV for Cu doped Nd2O3 nanoparticles which are higher than the bulk Nd2O3 (4.7 eV). This can be attributed to the quantum confinement effect of the nanoparticles. (C) 2012 Elsevier B.V. All rights reserved.

Theoretical and in vitro studies of a C-terminal peptide from PGKC of Leishmania mexicana mexicana

Trypanosomatids cause deadly diseases in humans. Of the various biochemical pathways in trypanosomatids, glycolysis, has received special attention because of being sequestered in peroxisome like organelles critical for the survival of the parasites. This study focuses on phosphoglycerate kinase (PGK) from Leishmania spp. which, exists in two isoforms, the cytoplasmic PGKB and glycosomal PGKC differing in their biochemical properties. Computational analysis predicted the likelihood of a transmembrane helix only in the glycosomal isoform PGKC, of approximate length 20 residues in the 62-residue extension, ending at, arginine residues R471 and R472. From experimental studies using circular dichroism and NMR with deuterated sodium dodecyl sulfate, we find that the transmembrane helix spans residues 448 +/- 2 to 476 in Leishmania mexicana PGKC. The significance of this observation is discussed in the context of glycosomal transport and substrate tunneling. (C) 2012 Elsevier B.V. All rights reserved.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Investigations on supersonic combustion in a combustion-driven shock tunnel

This article reports experimental results on supersonic combustion in a new facility. The facility is a combustion-driven shock tunnel, which is cheaper to build than the facilities in which such experiments are carried out conventionally. The observation region is a zone between two parallel flat plates with a 33 degrees wedge attached to the upstream end of the bottom plate. Gaseous hydrogen is injected at an angle of 45 degrees into an oncoming supersonic flow of Mach 2 (approximate) from a port on the bottom plate. The resulting flow field is visualized by a high speed camera in a dark background. Three different test gases, namely nitrogen, air, and oxygen-rich air are used, and the results are compared. A distinct luminosity due to combustion for oxygen-containing test gases is observed. Heat-transfer rates on a probe placed at the downstream end of the observation region and midway between the parallel plates are measured and compared for the three cases. Wall static pressure at 28 mm downstream of the injection port on the bottom plate is also presented.

Two-User Gaussian Interference Channel with Finite Constellation Input and FDMA

In the two-user Gaussian Strong Interference Channel (GSIC) with finite constellation inputs, it is known that relative rotation between the constellations of the two users enlarges the Constellation Constrained (CC) capacity region. In this paper, a metric for finding the approximate angle of rotation to maximally enlarge the CC capacity is presented. It is shown that for some portion of the Strong Interference (SI) regime, with Gaussian input alphabets, the FDMA rate curve touches the capacity curve of the GSIC. Even as the Gaussian alphabet FDMA rate curve touches the capacity curve of the GSIC, at high powers, with both the users using the same finite constellation, we show that the CC FDMA rate curve lies strictly inside the CC capacity curve for the constellations BPSK, QPSK, 8-PSK, 16-QAM and 64-QAM. It is known that, with Gaussian input alphabets, the FDMA inner-bound at the optimum sum-rate point is always better than the simultaneous-decoding inner-bound throughout the Weak Interference (WI) regime. For a portion of the WI regime, it is shown that, with identical finite constellation inputs for both the users, the simultaneous-decoding inner-bound enlarged by relative rotation between the constellations can be strictly better than the FDMA inner-bound.

Large nonlinear refraction and two photon absorption in ferroelectric Bi2VO5.5 thin films

Ferroelectric c-oriented Bi2VO5.5 (BVO) thin films (thickness approximate to 300 nm) were fabricated by pulsed laser deposition on corning glass substrates. Nonlinear refractive index (n(2)) and two photon absorption coefficient (beta) were measured by Z-scan technique at 532 nm wavelength delivering pulses with 10 ns duration. Relatively large values of n(2) = 2.05 +/- 0.2 x 10(-10) cm(2)/W and beta = 9.36 +/- 0.3 cm/MW were obtained for BVO thin films. Origin of the large optical nonlinearities in BVO thin films was discussed based on bond-orbital theory of transition metal oxides. (c) 2012 Elsevier B.V. All rights reserved.